Insecticidal guanidine derivatives

ABSTRACT

Novel guanidine derivatives of the formula (I) ##STR1## wherein Z is 2-chloro-5-pyridyl, 2-chloro-5-thiazolyl, or 3-chloro-5-isoxazolyl, 
     R 1  is hydrogen or C 1-4  alkyl, 
     R 2  is hydrogen, C 1-4  alkyl, C 3-4  alkynyl, C 3-4  alkenyl or 2-chloro-5-pyridylmethyl, 
     R 3  and R 4  each represent hydrogen, halogen, C 1-4  alkyl, C 3-1  alkynyl, C 3-4  alkenyl, benzyl which may be substituted, or Z--C(R 1 )H--, 
     n is 2 or 3, and 
     Y is nitro or cyano, 
     and pesticidal compositions comprising the compound of the formula (I) as active components.

The present invention relates to novel guanidine derivatives, to aprocess for the preparation, and to their use as insecticides.

It has already been disclosed that a certain group of guanidinederivatives is useful as insecticides (see Japanese Laid-open patentapplication No. 10762/1988).

There have been found novel guanidine derivatives of the formula (I)##STR2## wherein

Z represents 2-chloro-5-pyridyl, 2-chloro-5-thiazolyl or3-chloro-5-isoxazolyl,

R¹ represents hydrogen or C₁₋₄ alkyl,

R² represents hydrogen, C₁₋₄ alkyl, C₃₋₄ alkynyl, C₃₋₄ alkenyl or2-chlor-5-pyridylmethyl,

R³ and R⁴ each independently represents hydrogen, halogen, C₁₋₄ alkyl,C₃₋₄ alkynyl, C₃₋₄ alkenyl, optionally substituted benzyl orZ--C(R¹)H--,

n represents the integer 2 or 3, and

Y represents nitro or cyano.

The guanidine derivatives of the formula (I) are obtained when

a) compounds of the following formula (II) ##STR3##

wherein Z, R¹, R² and n has the same meanings as mentioned above,

are reacted with compounds of the formula (III) ##STR4##

wherein R³, R⁴ and Y have the same meanings as mentioned above,

in the presence of inert solvents.

The novel guanidine derivatives of the formula (I) exhibit powerfulinsecticidal properties.

Surprisingly, the guanidine derivatives according to the inventionexhibit a substantially greater insecticidal action than those knownfrom the above-mentioned Japanese Laid-open patent application.

Among the guanidine derivatives according to the invention of theformula (I), preferred compounds are those in which

Z represents 2-chloro-5-pyridyl or 2-chloro-5-thiazolyl,

R¹ represents hydrogen or methyl,

R² represents hydrogen, methyl, allyl, propargyl or2-chloro-5-pyridylmethyl,

R³ and R⁴ each independently represents hydrogen or methyl,

n represents the integer 2 or 3, and

Y represents nitro or cyano.

Very particularly preferred guanidine derivatives of the formula (I) arethose in which

Z represents 2-chloro-5-pyridyl or 2-chloro-5-thiazolyl,

R¹ represents hydrogen,

R² represents hydrogen or methyl,

R³ and R⁴ each represents hydrogen,

n represents the integer 2 or 3, and

Y represents nitro or cyano.

As specific examples of the compounds represented by the formula (I)according to the invention may be mentioned the following compounds:

1-{2-(6-chloro-3-pyridylmethylamino)ethyl}-2-nitroguanidine,

1-{2-(6-chloro-3-pyridylmethylamino)propyl}-2-nitroguanidine, and

1-{2-(2-chloro-5-thiazolylmethylamino)ethyl}-2-nitroguanidine.

If, for example, N-(6-chloro-3-pyridylmethyl)ethylenediamine and3-nitro-2-methylisothio urea are used as starting materials, the courseof the reaction can be represented by the following equation: ##STR5##In process a), the starting material of the formula (II) means compoundsbased on the above definitions of Z, R¹, R² and n, preferably compoundsbased on the above preferred definitions.

The starting materials of the formula (II) are known compounds disclosedby Japanese Laid-Open Patent application No.267561/1986 and 48680/1987,and as specific examples thereof may be mentioned:

N-(6-chloro-3-pyridylmethyl)-ethylene diamine,

N-(6-chloro-3-pyridylmethyl)-propylene diamine, and

N-(2-chloro-5-thiazolyl)-ethylene diamine.

In process a), the starting material of the formula (III) meanscompounds based on the above definitions of R³, R⁴ and Y, preferablycompounds based on the above preferred definitions.

The compounds of the formula (III) are well known in organic chemicalfield and, as specific examples, there may be mentioned.

3-nitro-2-methylisothiourea, and

3-cyano-2-methylisothiourea.

In carrying out the process a) mentioned above, use may be made, assuitable diluent, of any inert solvent.

Example of such diluents are water; aliphatic, cycloaliphatic andaromatic, optionally chlorinated, hydrocarbons such as pentane, hexane,cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene,dichloromethane, chloroform, carbon tetrachloride, ethylene chloride,chlorobenzene, dichlorobenzene, and the like; ethers such as diethylether, methyl ethyl ether, di-isopropyl ether, di-butyl ether, propyleneoxide, dimethoxyethane (DME), dioxane, tetrahydrofurane (THF) and thelike; nitriles such as acetonitrile, propionitrile, acrylonitrile, andthe like; alcohols such as methanol, ethanol, iso-propanol, butanol,ethylene glycol and the like; esters such as ethyl acetate, amylacetate, and the like; acid amides such as dimethyl formamide (DMF),dimethyl acetamide (DMA),N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA) andthe like; sulfones and sulfoxides such as dimethyl sulfoxide (DMSO),sulfolane and the like; and, bases, for example, such as pyridine.

In the above mentioned process a), the reaction temperatures can bevaried within a substantially wide range. In general, the reaction iscarried out at a temperature of from about -20° C. to about 100° C.,preferably from 10° C. to about 80° C.

Further, the reaction is carried out under normal pressure, although itis also possible to employ a higher or reduced pressure.

When the above mentioned process a) according to the present inventionis carried out, use is made, for example, of the above mentionedcompound (III) in the amount from 1.0 to 1.5 mols, preferably 1.0 to 1.1mols, per mol of the above mentioned compound (II), optionally in thepresence of inert solvents such as water, for example, to obtain thedesired compounds of the formula (I).

The active compounds of the formula (I) are well tolerated by plants,have a favorable level of toxicity to warm-blooded animals, and can beused for combating arthropod pests, especially insects which areencountered in agriculture, in forestry, in the protection of storedproducts and of materials, and in the hygiene field. They are activeagainst normally sensitive and resistant species and against all of somestages of development. The above-mentioned pests include:

from the class of the Isopoda, for example, Oniscus Asellus,Armadillidium vulgare and Porcellio scaber;

from the class of the Diplopoda, for example, Blaniulus guttulatus;

from the class of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.;

from the class of the Symphla, for example, Scuti gerella immaculata;

from the order of the Thysanura, for example, Lepisma saccharina;

from the order of the Collembola, for example, Onychiurus armatus;

from the order of the Orthoptera; for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migrato ria migratorioides,Melanoplus differentialis and Schistocerca gregaria;

from the order of the Dermaptera, for example, Forficula auricularia;

from the order of the Isoptera, for example, Reticulitermes spp.;

from the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.;

from the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.;

from the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci,

from the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma guadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.;

from the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia Oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.;

from order of the Lepidoptera, for example, Pectinophora gossypiella,Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella,Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria,Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella,Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Eariasinsulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolisflammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsapomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestiakuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana,Choristoneura fumiferana, Clysia ambiguella, Homona magnanima andTortrix viridana;

from the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelidesobtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsadecemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilussurinamensis, Anthonomus spp., Sitophilus spp., Otiorr hynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctusspp., Meligethes aeneus, Ptinus spp., Niptus hololenucus, Gibbiumpyslloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderusspp., Melolontha, Amphimallon solstitialis and Costelytra zealandica;

from the order of the Hymenoptera for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharanois and Vespa spp.;

from the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Cyrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,foams, pastes, granules, aerosols, natural and synthetic materialsimpregnated with active compound, very fine capsules in polymericsubstances, coating compositions for use on seed, and formulations usedwith burning equipment, such as fumigating cartridges, fumigating cansand fumigating coils, as well as ULV cold mist and warm mistformulations.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main,aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes,chlorinated aromatic or chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example mineral oilfractions, alcohols, such as butanol or glycol as well as their ethersand esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, or strongly polar solvents, such asdimethylformamide and dimethyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, corn cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products.

Dispersing agents include, for example, lignin sulphite waste liquorsand methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or lattices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulation.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts or iron, manganese boron,copper, cobalt, molybdenum and zinc. The formulations in general containfrom 0.1 to 95 percent by weight of active compound, preferably from 0.5to 90 percent by weight.

The active compounds according to the invention can be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, baits, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas, and substances produced by microorganisms.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agent are compounds which increase the action of theactive compounds, without it being necessary for the synergistic agentadded to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to100% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

EXAMPLE 1 ##STR6##

A mixture consisting of N-(6-chloro-3-pyridylmethyl) ethylenediamine(3.7 g), 3-nitro-2-methylisothiourea (2.7 g) and ethanol (20 ml) wasstirred at 30° C. until methylmercaptan ceased to be generatedtherefrom. After cooling, the separated crystals were taken out underfiltration, to obtain the desired1-{2-(6-chloro-3-pyridyl-methylamino)ethyl}-2-nitroguanidine. mp119°-122° C.

The following lists the product of Example 1 plus other compounds whichcan be prepared in the same way:

                                      TABLE 1                                     __________________________________________________________________________     ##STR7##                                                                     Comp.                                 Melting point                           No. Z        R.sup.1                                                                          R.sup.2      R.sup.3                                                                         R.sup.4                                                                         Y  n (°C.)                            __________________________________________________________________________         ##STR8##                                                                              H  H            H H NO.sub.2                                                                         2 119-122                                 2                                                                                  ##STR9##                                                                              H  H            H H NO.sub.2                                                                         3 136-140                                 3                                                                                  ##STR10##                                                                             H  H            H H NO.sub.2                                                                         2 122.5-123.5                             4                                                                                  ##STR11##                                                                             H  H            H H NO.sub.2                                                                         3                                         5                                                                                  ##STR12##                                                                             H  H            H H CN 2                                         6                                                                                  ##STR13##                                                                             H  H            H H CN 3                                         7                                                                                  ##STR14##                                                                             H  H            H H CN 2                                         8                                                                                  ##STR15##                                                                             CH.sub.3                                                                         H            H H NO.sub.2                                                                         2                                         9                                                                                  ##STR16##                                                                             H  n-C.sub.3 H.sub.7                                                                          H H NO.sub.2                                                                         2                                         10                                                                                 ##STR17##                                                                             H  i-C.sub.3 H.sub.7                                                                          H H NO.sub.2                                                                         2                                         11                                                                                 ##STR18##                                                                             H  t-C.sub.4 H.sub.9                                                                          H H NO.sub.2                                                                         2                                         12                                                                                 ##STR19##                                                                             H                                                                                 ##STR20##   H H NO.sub.2                                                                         2                                         13                                                                                 ##STR21##                                                                             H                                                                                 ##STR22##   H H NO.sub.2                                                                         2                                         14                                                                                 ##STR23##                                                                             H  CH.sub.2 CHCH.sub.2                                                                        H H NO.sub.2                                                                         2                                         15                                                                                 ##STR24##                                                                             H  CH.sub.2 C CH                                                                              H H NO.sub.2                                                                         2                                         16                                                                                 ##STR25##                                                                             H  CH.sub.2 C CH                                                                              H H NO.sub.2                                                                         3                                         17                                                                                 ##STR26##                                                                             H  H            H H NO.sub.2                                                                         2                                         __________________________________________________________________________

Biotest Example EXAMPLE 2 Biotest carried out against Nephotattixcincticeps (green rice leafhopper) exhibiting resistance toorganophosphorus and carbamate insecticides

Preparation of test formulation:

solvent: 3 parts by weight of xylene

Emulsifier: 1 part by weight of polyoxyethylenealkylphenyl-ether

To prepare suitable formulations of the active compounds, 1 part byweight of each of the active compounds was mixed with theabove-mentioned amount of the solvent containing the above-mentionedamount of the emulsifier, and the mixture was diluted with water to thepredetermined concentration.

Test Method:

Use was made of a plurality of pots each having a diameter of 12 cm inwhich were planted rice plant seedlings each having a height of about 10cm. Onto each rice-plant seedling there were sprayed 10 ml of an aqueoussolution of the active compound as prepared above and having apredetermined concentration. After the sprayed solution was dried, eachof the pots was covered with a metallic net having a diameter of 7 cmand height of 14 cm, in which 30 female adults or Nephiotettixcincticeps exhibiting resistance to organophosphorus and carbamateinsecticides were released, and then each pot was placed in a constanttemperature chamber. After two days, the number of killed insects wasdetermined to obtain the insect mortality.

EXAMPLE 3 Test on planthoppers exhibiting resistance to organophosphorusand carbamate insecticides

Test Method:

Use was made of a plurality of pots each having a diameter of 12 cm inwhich were planted rice plant seedlings each having a height of about 10cm. Onto each of the potted rice-plant seedlings there was sprayed ml ofan aqueous solution of the active compound having a predeterminedconcentration, prepared in similar manner to Example 2. After thesprayed solution dried, each pot was covered with a metallic net havinga diameter of 7 cm and a height of 14 cm, into which were released 30female adults of brown planthoppers (Nilaparvata lugens) exhibitingresistance to organophosphorus and carbamate insecticides, and then eachpot was placed in a constant temperature chamber. After two days, thenumber of killed insects was determined to obtain the insect mortality.

In similar manner mortality was determined on each of Sezirounka(white-backed planthopper, Sogatella furcifera) and Himetobiunka(smaller blown planthopper, Laodelphax striatellus) having resistance toorganophosphorus pesticides.

In the above-mentioned Test Examples 2 and 3, use was made, as therepresentative examples of the active compounds represented by formula(I), of compounds 1, 2 and 3 in Table 1, each exhibting 100% mortalityat a concentration of active material.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. A guanidine derivative of the formula ##STR27## wherein Zis 2-chloro-5-pyridyl,R¹ is hydrogen or C₁₋₄ alkyl, R² is hydrogen, C₁₋₄alkyl, C₃₋₄ alkynyl, C₃₋₄ alkenyl or 2-chloro-5-pyridylmethyl, R³ ishydrogen, halogen, C₁₋₄ alkyl, C₃₋₄ alkynyl, C₃₋₄ alkenyl, benzyl orZ--C(R¹)H--, R⁴ is hydrogen, halogen, C₁₋₄ alkyl, C₃₋₄ alkynyl, C₃₋₄alkenyl, benzyl or Z--C(R¹)H--, n is 2 or 3, and Y is nitro or cyano. 2.A compound according to claim 1, whereinR¹ is hydrogen or methyl, R² ishydrogen, methyl, allyl, propargyl or 2-chloro-5-pyridylmethyl, R³ ishydrogen or methyl, R⁴ is hydrogen or methyl, n is 2 or 3, and Y isnitro or cyano.
 3. A compound according to claim 1, whereinZ is2-chloro-5-pyridyl, R¹ is hydrogen, R² is hydrogen or methyl, R³ ishydrogen, R⁴ is hydrogen, n is 2 or 3, and Y is nitro or cyano.
 4. Acompound according to claim 1, wherein such compound is1-{2-(6-chloro-3-pyridyl-methylamino)ethyl}-2-nitroguanidine of theformula ##STR28##
 5. A compound according to claim 1, wherein suchcompound is1-{3-(6-chloro-3-pyridyl-methylamino)propyl}-3-nitroguanidine of theformula ##STR29##
 6. An insecticidal composition comprising aninsecticidally effective amount of a compound according to claim 1 and adiluent.
 7. A method of combatting insects which comprises applying tosuch insects or to an insect hatitat an insecticidally effective amountof a compound according to claim
 1. 8. The method according to claim 7,wherein such compoundis1-{2-(6-chloro-3-pyridyl-methylamino)ethyl}-2-nitroguanidine or1-{3-(6-chloro-3-pyridyl-methylamino)propyl}-3-nitroguanidine.